Graphitic carbon nitride (g-C3N4) was prepared using a simple method. Activated carbon (AC) was used to support the g-C3N4 catalyst. Catalytic evaluation indicated that the g-C3N4/AC catalyst had enhanced catalytic activity for acetylene hydrochlorination as a non-metallic catalyst when compared to AC. X-ray photoelectron spectra confirmed the presence of nitrogen and carbon species in the prepared g-C3N4/ AC catalysts. Temperature-programed decomposition results indicated that hydrogen chloride was notably well adsorbed onto g-C3N4/AC catalysts. Theoretical calculations indicated that hydrogen chloride is adsorbed at the nitrogen atom and that acetylene is adsorbed at the carbon atom of g-C3N4. The transfer of a proton from the nitrogen atom to the chloroethenyl moiety is the rate-limiting step. The combination of activation of both reactants and facile product desorption makes g-C3N4 an interesting catalyst for acetylene hydrochlorination. Crown Copyright (C) 2013 Published by Elsevier Inc. All rights reserved.